CN103469263B - Electroplating deposition prepares the method for nanocrystalline structure silver tin alloy coat - Google Patents
Electroplating deposition prepares the method for nanocrystalline structure silver tin alloy coat Download PDFInfo
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- CN103469263B CN103469263B CN201310404950.6A CN201310404950A CN103469263B CN 103469263 B CN103469263 B CN 103469263B CN 201310404950 A CN201310404950 A CN 201310404950A CN 103469263 B CN103469263 B CN 103469263B
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Abstract
The invention belongs to electronics finishing and prepare alloy layer field, be specifically related to the method that electroplating deposition prepares nanocrystalline structure silver tin alloy coat.Adopt 1-butyl-3-methyl imidazolium tetrafluoroborate ([BMIM] [BF
4]) ionic liquid is as electroplate liquid solvent, tin protochloride and Silver Nitrate, as main salt, are mixed with electroplate liquid, and electroplating deposition obtains the nanocrystalline Ag-Sn alloy layer that grain-size is less than 20nm.Raw material disclosed by the invention is common to be easy to get, and preparation technology is easy should go.Preparation method disclosed by the invention does not limit by region, has the advantages such as energy-conserving and environment-protective, is applicable to large-scale commercial production.
Description
Technical field
The invention belongs to the Technology field of plating alloy coating, be specifically related to a kind of method adopting electroplating deposition to prepare nanocrystalline structure silver tin (Ag-Sn) alloy layer in ionic liquid.
Background technology
In the process of electronic product to unleaded adjustment, be convenient to process, environmental protection and reliably lead-free alloy coating play keying action.Yin Xi (Ag-Sn) alloy layer has that resistance is low, hardness is high, bonding strength is high and good, the good anti-tin of heat-resistant anti-fatigue characteristic must the feature such as energy for growth, can be used for the sub-apparatus of Portable power and high reliability parts, be current very one of solderable coating having application prospect, be more and more subject to people's attention.
Electroplating deposition technique has very large advantage in preparation Ag-Sn alloy layer, but traditional electrical plated deposition is prepared Ag-Sn alloy layer and is all needed to carry out in specific water-soluble electrolyte, in water-soluble solution, larger (silver-colored standard potential in 25 ° of C aqueous solution is 0.799V to the normal potential difference of Ag and Sn, the standard potential of tin in 25 ° of C aqueous solution is-0.136V), realize Ag-Sn codeposition, keep component content in alloy layer constant, improve Ag component content in coating very difficult, if the people such as N.Kanek are containing sulphur arteries and veins and a small amount of N, in the sulfate bath of the two polyoxyethylene stearylamine of N-, only obtain the alloy layer that Ag massfraction is 2% ~ 5%, the people such as YFujiwara are containing SnSO
4, AgNO
3, K
4p
20
7dC electrodeposition mode is adopted to obtain Ag-Sn composite deposite with in the alkali plating solution of polyoxyethylene glycol (PEG6000), in wider current density range, in coating, the massfraction of Ag nano particles remains on about 4%, and skewness, the visible content obtaining silver in Ag-Sn alloy layer in water-soluble electrolyte liquid system maintains lower numerical value, United States Patent (USP) (US5514261) adopts two ammonia complexs of Silver Nitrate or silver, stannous salt or tetravalence pink salt, mercaptoalkyl carboxylic acid and mercaptoalkylsulfonic acid are as non-cyanide silver electroplating-tin alloy electrolytes, from silver-tin alloy coat that this bath deposition goes out, the massfraction of silver is 20% ~ 99%, in the visible Ag-Sn alloy layer obtained in water-soluble electrolyte liquid system, the component content of silver is unstable, in fact, the coating microstructure composition that water-soluble bath system obtains and solution composition, additive, pH value, current density, temperature and stirring etc. are related, the change of each parameter strictly must be controlled during plating, and maintain in stable scope, this brings certain difficulty also can to actual production technique.
In addition, water-soluble Ag-Sn alloy plating liquid generally all have severe corrosive or for severe toxicity have cyanogen formula, in operation, usually discharge a large amount of gas, liquid, solid waste, serious harm is caused to environment and operator, as the people such as Sang-Su-Ha adopt the silver-colored cyanogen complex salt coordinated with prussiate by single salt of silver as main salt electroplating deposition Ag-Sn alloy, the people such as Kubota.N have cyanogen process formula with silver potassium cyanide and stannous pyrophosphate for main salt sedimentation Ag-Sn alloy, find that in alloy layer, Theil indices is different different with pH value, alloyed layer character is not identical yet, in the scope of PH9 ~ 10, when in alloy layer, tin codeposition amount is greater than 17%, in alloy layer, surface is in canescence, bonding force difference also has and burns phenomenon.The people such as Vyacheslavov also obtain almost identical result when prussiate-pyrophosphate salt tank liquor electrosilvering tin alloy, and these techniques, owing to using the prussiate having hypertoxicity in a large number, are very limited.Therefore, be badly in need of a kind of novel bath system of exploitation, solve exist in water-soluble Ag-Sn alloy electroplating bath system Ag-Sn codeposition difficulty, silver content is on the low side in coating, has cyanogen to fill a prescription the problems such as contaminate environment.
Summary of the invention
For the shortcoming existed in current water-soluble silver tin (Ag-Sn) alloy electroplating bath system technique, in order to solve that current electroplating deposition prepares that silver-colored tin (Ag-Sn) alloy layer technique exists have cyanogen severe toxicity, component content is unstable in alloy layer, the problems such as in coating Ag component content is low, the invention provides a kind of method that electroplating deposition prepares nanocrystalline structure silver tin alloy coat.
The concrete preparation manipulation step of the inventive method is as follows:
(1) 15 ~ 50 grams of tin protochlorides and 20 ~ 30 grams of silver nitrate crystals are dissolved in 1000ml ion liquid solvent, be heated to temperature 60 ° of C, magnetic agitation 1.5 hours, be made into the ionic liquid saturated solution of argentiferous tin, leave standstill and be cooled to room temperature, get supernatant liquid stand-by;
(2) under room temperature, in 500ml supernatant liquid, slowly add 10 ~ 100ml polyoxyethylene glycol while stirring, stir 1 ~ 3 hour, adding ammoniacal liquor adjustment pH value is 8 ~ 9, adds 50 grams of thiocarbamides, stirs, obtain electrolytic solution; Wherein the speed that adds of polyoxyethylene glycol is 0.2 ~ 1ml/min;
(3) using platinum titanium net as anode, latten(-tin), as negative electrode, adds above-mentioned electrolytic solution in plating tank, carries out electroplating deposition; Plating voltage is 0.8 ~ 3.5V, temperature is room temperature ~ 70 ° C, plating time is 0.5 ~ 2h, electroplating deposition, latten(-tin) is formed Yin Xi (Ag-Sn) alloy layer of nanocrystalline structure, and in Yin Xi (Ag-Sn) alloy layer, the massfraction of silver (Ag) is 24 ~ 32%.
Described ion liquid solvent is 1-butyl-3-methyl imidazolium tetrafluoroborate ([BMIM] [BF
4]).
Described nanocrystalline grain-size is less than 20nm.
In order to improve metal-salt at 1-butyl-3-methyl imidazolium tetrafluoroborate ([BMIM] [BF
4]) solubleness in ionic liquid, by tin protochloride (SnCl
22H
2and Silver Nitrate (AgNO O)
3) dissolution of crystals in 1000ml ion liquid solvent, be heated to temperature 60 ° of C, magnetic agitation 1.5 hours, be made into the ionic liquid saturated solution of argentiferous tin; Consider ionic liquid saturated solution good solubility in polyoxyethylene glycol, the present invention slowly adds polyoxyethylene glycol (PEG) as additive in ionic liquid saturated solution, give full play to the effect of its stablizer and dispersion agent, the combination complexing agent adding ammoniacal liquor and sulfocompound (thiocarbamide) is intended to reduce silver ions (Ag
+) redox potential, to reduce the difference of the redox potential between Sn and Ag, also play silver ions (Ag
+) preferential complexing action, keep silver ions (Ag in electrolytic solution
+) stability.
The invention has the advantages that: raw material disclosed by the invention is common to be easy to get, main salt component is simple, and preparation is convenient, containing corrosives and preparation technology is easy should go, adopts [BMIM] [BF
4] ionic liquid is as reaction solvent, can prepare and have the controlled Yin Xi of component (Ag-Sn) alloy layer, in coating, the component concentration of silver maintains 24%-32%, and crystal grain is evenly distributed, and size is less than 20nm.
Accompanying drawing explanation
Fig. 1 is the transmission electron micrograph of the Ag-Sn alloy layer obtained of the embodiment of the present invention 1.
Fig. 2 is the transmission electron micrograph of the Ag-Sn alloy layer obtained of the embodiment of the present invention 2.
Fig. 3 is the cross-sectional scans electromicroscopic photograph of the Ag-Sn alloy layer obtained of the embodiment of the present invention 3.
Embodiment
Below in conjunction with embodiment, the present invention is further described.
embodiment 1:
The concrete operation step that electroplating deposition prepares nanocrystalline structure silver tin alloy coat is as follows:
1. by 15 grams of tin protochloride (SnCl
22H
2o) and 20 grams of Silver Nitrate (AgNO
3) dissolution of crystals in 1000ml ion liquid solvent, be heated to temperature 60 ° of C, magnetic agitation 1.5 hours, be made into the ionic liquid saturated solution of argentiferous tin, leave standstill be cooled to room temperature, get supernatant liquid 500ml stand-by; Described ion liquid solvent is 1-butyl-3-methyl imidazolium tetrafluoroborate ([BMIM] [BF
4]);
2. under room temperature, in 500ml supernatant liquid, slowly add 10ml polyoxyethylene glycol while stirring, it is 0.2ml/min that polyoxyethylene glycol adds speed; Stir 1 hour, adding ammoniacal liquor adjustment pH value is 8, adds 50 grams of thiocarbamides, stirs, obtain electrolytic solution;
3., using platinum titanium net as anode, latten(-tin), as negative electrode, adds above-mentioned electrolytic solution in plating tank, carries out electroplating deposition; Before plating, latten(-tin) carries out polishing, polishing, oil removing, acid corrosion, washing and drying process; Plating voltage is 0.8V, and temperature is room temperature, and plating time is 0.5h, and after electroplating deposition, form Yin Xi (Ag-Sn) alloy layer of nanocrystalline structure at latten(-tin), in Yin Xi (Ag-Sn) alloy layer, the massfraction of silver (Ag) is 32%; The latten(-tin) washed with methanol three times of Yin Xi (Ag-Sn) alloy layer will be had, again with washed with de-ionized water once, dry under temperature 60 ° of C, coating transmission electron micrograph as shown in Figure 1, can find out, in coating product, nanocrystal size distribution is even, and average grain size is about 18nm, is less than 20nm.
embodiment 2:
The concrete operation step that electroplating deposition prepares nanocrystalline structure silver tin alloy coat is as follows:
1. by 30 grams of tin protochlorides, 25 grams of silver nitrate crystals are dissolved in 1000ml ion liquid solvent, are heated to temperature 60 ° of C, magnetic agitation 1.5 hours, are made into the ionic liquid saturated solution of argentiferous tin, leave standstill after being cooled to room temperature that to get supernatant liquid 500ml stand-by; Described ion liquid solvent is 1-butyl-3-methyl imidazolium tetrafluoroborate ([BMIM] [BF
4]);
2. under room temperature, in 500ml supernatant liquid, slowly add 50ml polyoxyethylene glycol while stirring, it is 0.5ml/min that polyoxyethylene glycol adds speed; Stir 2 hours, adding ammoniacal liquor adjustment pH value is 9, adds 50 grams of thiocarbamides, stirs, obtain electrolytic solution;
3., using platinum titanium net as anode, latten(-tin), as negative electrode, adds above-mentioned electrolytic solution in plating tank, carries out electroplating deposition; Before plating, latten(-tin) carries out polishing, polishing, oil removing, acid corrosion, washing and drying process, plating voltage is 1.8V, temperature is 50 ° of C, plating time is 1h, after electroplating deposition, form Yin Xi (Ag-Sn) alloy layer of nanocrystalline structure at latten(-tin), in Yin Xi (Ag-Sn) alloy layer, the massfraction of silver (Ag) is 28%; The latten(-tin) washed with methanol three times of Yin Xi (Ag-Sn) alloy layer will be had, then with washed with de-ionized water once, dry under temperature 75C, coating transmission electron micrograph as shown in Figure 2, can find out, in coating product, nanocrystalline particle size distribution is even, and average grain size is about 8nm.
embodiment 3:
The concrete operation step that electroplating deposition prepares nanocrystalline structure silver tin alloy coat is as follows:
1. 50 grams of tin protochlorides and 30 grams of silver nitrate crystals are dissolved in 1000ml ion liquid solvent, are heated to 60 ° of C, magnetic agitation 1.5 hours, be made into the ionic liquid saturated solution of argentiferous tin, leave standstill after being cooled to room temperature that to get supernatant liquid 500ml stand-by; Described ion liquid solvent is 1-butyl-3-methyl imidazolium tetrafluoroborate ([BMIM] [BF
4]);
2. under room temperature, in 500ml supernatant liquid, slowly add 100ml polyoxyethylene glycol while stirring, it is 1ml/min that polyoxyethylene glycol adds speed; Stir 3 hours, adding ammoniacal liquor adjustment pH value is 9, adds 50 grams of thiocarbamides, stirs, obtain electrolytic solution;
3., using platinum titanium net as anode, latten(-tin), as negative electrode, adds above-mentioned electrolytic solution in plating tank, carries out electroplating deposition; Before plating, latten(-tin) carries out polishing, polishing, oil removing, acid corrosion, washing and drying process, plating voltage is 3.5V, temperature is 70 ° of C, plating time is 2h, after electroplating deposition, form Yin Xi (Ag-Sn) alloy layer of nanocrystalline structure at latten(-tin), in Yin Xi (Ag-Sn) alloy layer, the massfraction of silver (Ag) is 24%; The latten(-tin) washed with methanol three times of Yin Xi (Ag-Sn) alloy layer will be had, then with washed with de-ionized water once, dry under temperature 90 ° of C.Its cross sectional scanning electron Photomicrograph as shown in Figure 3, can find out that coating product production is fine and close.
Claims (2)
1. electroplating deposition prepares the method for nanocrystalline structure silver tin alloy coat, it is characterized in that preparation manipulation step is as follows:
(1) 15 ~ 50 grams of tin protochlorides and 20 ~ 30 grams of silver nitrate crystals are dissolved in 1000mL ion liquid solvent, be heated to temperature 60 C, magnetic agitation 1.5 hours, be made into the ionic liquid saturated solution of argentiferous tin, leave standstill and be cooled to room temperature, get supernatant liquid stand-by; Described ion liquid solvent is 1-butyl-3-methyl imidazolium tetrafluoroborate;
(2) under room temperature, in 500mL supernatant liquid, slowly add 10 ~ 100mL polyoxyethylene glycol while stirring, stir 1 ~ 3 hour, adding ammoniacal liquor adjusted to ph is 8 ~ 9, adds 50 grams of thiocarbamides, stirs, obtain electrolytic solution; Wherein the speed that adds of polyoxyethylene glycol is 0.2 ~ 1mL/min;
(3) using platinum titanium net as anode, latten(-tin), as negative electrode, adds above-mentioned electrolytic solution in plating tank, carries out electroplating deposition; Plating voltage is 0.8 ~ 3.5V, temperature is room temperature ~ 70 DEG C, plating time is 0.5 ~ 2h, electroplating deposition, latten(-tin) is formed Yin Xi (Ag-Sn) alloy layer of nanocrystalline structure, and in Yin Xi (Ag-Sn) alloy layer, the massfraction of silver (Ag) is 24 ~ 32%.
2. electroplating deposition according to claim 1 prepares the method for nanocrystalline structure silver tin alloy coat, it is characterized in that: described nanocrystalline grain-size is less than 20nm.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101802262A (en) * | 2007-08-06 | 2010-08-11 | 勒芬天主教大学 | deposition from ionic liquids |
| CN103173795A (en) * | 2012-03-27 | 2013-06-26 | 上海域高环境技术有限公司 | Electroplating method |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101802262A (en) * | 2007-08-06 | 2010-08-11 | 勒芬天主教大学 | deposition from ionic liquids |
| CN103173795A (en) * | 2012-03-27 | 2013-06-26 | 上海域高环境技术有限公司 | Electroplating method |
Non-Patent Citations (3)
| Title |
|---|
| 在离子液体[EMIm]BF4中Sn(Ⅱ)、Sb(Ⅲ)电化学还原的研究;杨文忠等;《现代化工》;20071130;第27卷;第203-206页 * |
| 室温离子液体中银纳米微粒的制备与结构表征;张晟卯等;《物理化学学报》;20040531;第20卷(第5期);第554-556页 * |
| 离子液体中电沉积金属的研究现状;王晓丹等;《材料导报》;20081031;第22卷(第10期);第70-75页 * |
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